Crystalline modification of fipronil

ABSTRACT

The present invention relates to a crystalline modification of fipronil, to a process for the preparation of the same, to pesticidal and parasiticidal mixtures and compositions comprising said crystalline modification and to their use for combating pests and parasites.

This application is a National Stage application of International Application No. PCT/EP2007/061896 filed Nov. 5, 2007, the entire contents of which is hereby incorporated herein by reference. This application also claims the benefit under 35 U.S.C. §119 of European Patent Application No. 06023437.4, filed Nov. 10, 2006, the entire contents of which is hereby incorporated herein by reference.

The present invention relates to a novel crystalline modification of fipronil, to a process for the preparation of the same, to pesticidal and parasiticidal mixtures and compositions comprising said crystalline modification and to their use for combating pests and parasites.

Fipronil (formula I) is an active compound for controlling certain insect and acarid pests, and parasites.

Various processes for the preparation of fipronil have been described, generally and in detail. Documents which give detailed preparation procedures are e.g. EP 295 117; EP 460 940; EP 484 165; EP 668 269; EP 967 206; EP 1 331 222; EP 0 374 061; U.S. Pat. No. 5,631, 381; CN 1374298; or J. of Heibei University of Science and Technology, Vol. 25 (2), Sum 69 (2004), Dok. Serial No. 1008-1542 (2004) 02-0018-03.

Characterization of the fipronil material obtained by the processes described in the prior art is usually done by ¹H-NMR analysis and/or measurement of the melting point. The described melting points are in the range of from 187° C. to 203° C., mostly in the range of from 195° C. to 203° C. In the Pesticidal Manual, 13th Edition (2003), British Crop Protection Council, p. 433, fipronil is described as a white solid with a melting point of 200 to 201° C., with technical fipronil having a melting point of 195.5° C. to 203° C. Observations of different crystalline forms of fipronil have not been described, let alone any characterization of a certain crystalline modification or a preparation procedure for obtaining a certain crystalline modification.

For the large-scale preparation and formulation of a market compound such as fipronil, it is of crucial importance to know whether different crystalline modifications (also frequently referred to as polymoprhs) of a compound exist, how they can be obtained, and what their characteristic properties are. Crystalline modifications of one compound may have very different properties, for example with regard to solubility, rate of dissolution, suspension stability, stability during grinding, vapour pressure, optical and mechanical properties, hygroscopicity, crystal size, filtration properties, desiccation, density, melting point, degradation stability, stability against phase transformation into other crystalline modifications, colour, and even chemical reactivity.

For example, different crystalline modifications frequently manifest themselves in different forms of the crystals, such as needles or plates. This is of relevance for e.g a filtration step in the preparation procedure. Plates typically will clog the pores of a filter leading to loss of time and product and tedious and expensive cleaning work. Also, a crystalline modification being present as plates and a crystalline modification being present as needles can have significantly different bulk densities which has implications for storage and packaging. Another relevant aspect, especially in the production of pesticides, is whether the crystalline modification is present as a fine powder which can produce hazardous dusts, or as dust-free larger crystals.

Against this background, it has been an object of the present invention to find and characterize a novel crystalline modification of fipronil.

A further object has been to find preparation procedures for the novel crystalline modification which reproducibly give the crystalline modification.

Another object of the invention has been to find preparation procedures which give the novel crystalline modification II in high yield.

Yet another object of the invention has been to find preparation procedures which give the novel crystalline modification essentially excluding other crystalline modification forms (i.e. in over 80% by weight).

Accordingly, a novel crystalline modification of fipronil, a process for its preparation, pesticidal and parasiticidal mixtures and compositions comprising it and its use for combating pests and parasites has been found. The novel crystalline modification of fipronil is defined as “novel crystalline modification II” throughout this application. It is present as long needles which provides for its easy filtration.

Also, most suprisingly, 3 other crystalline modifications of fipronil have been found, which are subject to co-pending patent applications. Especially surprising was that the present crystalline modification II of fipronil does not melt but rather undergoes a phase transformation during heating into two thermodynamically more stable forms I and V and/or a mixture of them, and thus in a typical melting point measurement will give the melting points of these forms I and V or mixtures of them. Crystalline modification I has a very similar melting point as a second crystalline modification V (as described in co-pending patent applications), both melting points lying in the range of the melting points given in the prior art (i.e. 195 to 203° C.). Moreover, one further crystalline modification IV of fipronil, as described in a co-pending patent application, also undergoes a phase transformation. The solid forms of fipronil thus are part of a very complex crystallization scenario. It can be concluded that the melting points given in the literature in no way can indicate which crystalline modification or crystalline modification mixtures were analyzed.

In T 605/02, the Technical Board of Appeal of the European Patent Authority ruled that, in the absence of a respective described preparation procedure, even the XRD pattern of a certain crystalline modification does not constitute prior art for lack of enablement. Thus, melting points given in documents published prior to the filing of this application cannot be regarded as prior art for the present invention as they do not enable the artisan to prepare the novel crystalline modification of fipronil.

Crystalline modification II of fipronil, in an X-ray powder diffractogram at 25° C., shows at least 4, in particular at least 5, especially 7 and preferably all of the following reflexes:

(1) d = 13.44 ± 0.2 Å 2Θ = 6.6 ± 0.2° (2) d = 7.84 ± 0.1 Å 2Θ = 11.3 ± 0.2° (3) d = 5.50 ± 0.07 Å 2Θ = 16.1 ± 0.2° (4) d = 5.14 ± 0.05 Å 2Θ = 17.2 ± 0.2° (5) d = 4.95 ± 0.05 Å 2Θ = 17.9 ± 0.2° (6) d = 3.95 ± 0.05 Å 2Θ = 22.4 ± 0.2° (7) d = 3.77 ± 0.05 Å. 2Θ = 23.5 ± 0.2° (8) d = 3.22 ± 0.03 Å 2Θ = 27.6 ± 0.2° (9) d = 2.91 ± 0.03 Å 2Θ = 30.8 ± 0.2°.

In a particularly preferred embodiment, the crystalline modification II exhibits a powder X-ray diffraction pattern substantially the same as the pattern shown in FIG. 1.

Studies of single crystals of the crystalline modification II have shown that the crystal system is monoclinic and has the space group P 2(1)/c. The characteristic data of the crystal structure of the crystalline modification II are shown in Table 1:

TABLE 1 Crystallographic data and parameters of the crystalline modification II measured from Parameter Modification II Class Monoclinic Space group P 2(1)/c a  8.606(1) Å b 26.919(2) Å C 16.086(1) Å α 90° β 102.066(1)° γ 90° Volume 3644.0(3) Å³ Z 4 Temperature −173.2° C. Density (calculated) 0.94 g/cm^(3a) R1, ωR2 0.081, 0.222 a, b, c = Length of the unit cell edges α, β, γ = Angles of the unit cell Z = Number of molecules in the unit cell ^(a)Density calculated without the incorporated solvent

The single crystal structure further reveals, that modification II of fipronil has channel like tubes running through the crystal. These tubes are occupied by the corresponding crystallization solvent. This affects the powder diffraction patterns in a way that the X-ray reflections can be seen at slightly different 2Theta and d-spacing values (not more than ±0.34° 2Theta) for many of the solvates. The peak intensities are independent of the incorporated solvent[_(B1)]. Modification II can therefore be regarded as a solvate of the corresponding co-crystallized solvent.

As the solvents trapped in the crystal are removed, the crystalline modification II of fipronil undergoes an endothermic phase transformation. In a differential scanning calorimetry, DSC, measurement (heating rate 5 K/min) this is observed typically at around 130° C., with an onset at 100 to 110° C. and completion at 138° C. to 145° C. This phase transformation leads to crystalline modifications I and V and/or depending on the heating rate to mixtures of them. We give here as an example a differential scanning calorimetry (DSC) thermogram of the crystalline modification II of fipronil, recorded with 10 K/min. It further contains two endotherms with maxima at 196° C. and 203° C., representing the melting points of the crystalline modifications I (mp. 196° C.) and V (mp. 203° C.) of fipronil. It is shown in FIG. 2.

Solvents in the process for preparation of modification II are inert and consist mainly of benzene derivatives, such as benzene, which may be substituted by one or more groups selected from halogen, cyano, C₁-C₆-alkyl, C₁-C₆-alkoxy, halogenmethyl, and nitro, and other solvents, such as tetrahydrofuran (THF), 1,2-dichloroethane, and acetonitrile. Preferred benzene derivatives are fluorobenzene, benzonitrile, anisole, p-xylene, o-xylene, m-xylene, CF₃-benzene, n-butylbenzene, t-butylbenzene, s-butyl-benzene, i-butylbenzene, chlorobenzene, 2-chlorotoluene, 4-chlorotoluene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,4-diisopropylbenzene, mesitylene, nitrobenzene, 4-nitrotoluene, n-propylbenzene, and toluene, and more preferably selected from mono-, di- or tri(C₁-C₆-alkyl) benzenes[_(B2)], which may be halogenated.

The crystalline modification II of fipronil can be achieved preferably from the following solvents; tetrahydrofuran, 1,2-dichloroethane, acetonitrile, toluene, mono chloro benzene, 1,2-dichlorobenzene, ethyl benzene, mesitylene, nitrobenzene and CF₃-benzene.

The amount of co-crystallized solvent depends of the properties, such as size of the corresponding solvent. For toluene the maximum amount of solvent in the crystals is in the range of 5 w-%. The solvent amount can be analysed for example via thermogravimetry. A TGA-trace of crystalline fipronil modification II from toluene is shown in FIG. 3.

In addition to the various solvent adduct versions of modification II, it was further discovered, that from all of the above mentioned solvents also at least one other crystalline modification can be achieved via solvent crystallization. Several conditions lead also to mixtures of forms, but also polymorph or modification pure material can be prepared by applying delicate and controlled, solvent dependant methods. The applicant has described preparation methods of modifications I and V in co-pending patent applications[_(B3)].

Also a further modification F-ST, a toluene solvate, is described in WO2007/069254. This solvate modification F-ST is different from the here described novel modification II which also contains co-crystallized toluene. This should be made clear by comparison of the powder diffraction patterns[_(B4)] shown in FIG. 1, and in WO2007/069254. It appears that F-ST is a stoichiometric solvate of fipronil and toluene in the ratio of about 2:1 respectively. In the case of toluene this means that there is about 8 w-% of toluene in the crystal lattice, which is about 3 w-% more than for crystalline modification II according to the current invention.

Further, structurally similar solvates to F-ST form can be prepared also with benzene, mono chloro benzene (MCB) as well as xylene (mixture).

Similar to F-ST, also crystalline modification II of fipronil can be used as starting material to prepare pure modification V via drying (tempering) above 100° C., preferably above 130° C. The drying time depends of the applied pressure. As modification II contains less toluene than F-ST, also less energy is needed in the drying (tempering) process.

In another embodiment, the present invention relates to the crystalline modification II having a fipronil content of at least 92% by weight, particularly at least 96% by weight and especially at least 98% by weight.

This invention also relates to solid (compositions of) fipronil comprising the crystalline modification II as defined hereinabove and a form of fipronil being different from said crystalline modification II (herein also referred to as “fipronil form”), e.g. amorphous fipronil or fipronil of a crystalline modification different from crystalline modification II. Preferably, the solid (compositions of) fipronil comprise the crystalline modification II in at least 85% by weight, preferably in at least 90% by weight, more preferably in at least 95% by weight, and most preferably in at least 98% by weight[_(B6)].

The crystalline modification II can be prepared using a process which comprises the following steps:

-   -   step i) preparing a solution of a solid form of fipronil being         different from the crystalline modification II in a solvent S         preferably selected from tetrahydrofurane (THF),         1,2-dichloroethane (DCE), acetonitrile, toluene,         monochlorobenzene (MCB), 1,2-dichlorobenzene (DCB), ethyl         benzene, mesitylene, nitrobenzene and CF₃-benzene;     -   step ii) effecting crystallization of fipronil; and     -   step iii) isolating the resulting precipitate.

The preparation of modification II is favored by crystallization from concentrated solutions at elevated temperatures. Further, the resulting modification is dependent of especially the nucleation temperature followed by the formation of the first crystals. The beginning of the crystallization can be detected visually as clouding of the crystallization solution and/or with the aid of a turbidity probe. Usually the evaporation or cooling crystallisation is effected not above 130° C., or close to the boiling point of the used solvent, and preferably not below 80° C.

Thus crystallization of modification II can be done by crystallization of fipronil from the aforesaid solvents at constant temperature by evaporation and/or by adding at least a polar solvent P to the above mentioned aromatic solvents. Such cooling cystallisation is advantageously started at a temperature close to the boiling point of the solvent, however, preferably not above 130° C. or below 80° C. More precisely in the cases of THF, 1,2-dichloroethane and acetonitrile the crystallization temperature in an evaporation crystallization should be kept within a temperature window of 30 and 55° C., for toluene within a temperature window of 90° C. to 110° C., for MCB and 1,2-dichlorobenzene in between 70° C. and 130° C., nitrobenzene and mesitylene in between 90° C. and 130° C. and for ethyl benzene in between 100° C. and 130° C. and for CF₃-benzene in between 90° C. and 103° C.

Modification II can also be crystallised from mixtures of the above mentioned aromatic solvents and polar solvents P, advantageously in amounts up to 20 vol.-%, preferably 5 to 15 vol.-% of P. Such solvent P is preferably selected from the group of methanol, ethanol, propan-1-ol, propan-2-ol (isopropanol), butan-1-ol (n-butanol), butan-2-ol, tert-butanol, 2-methyl-propan-1-ol (iso-butanol), 2-methyl-propan-2-ol, pentan-3-ol, 2-methyl butan-1-ol, 3-methyl butan-1-ol, 1,2-ethanediol, 1,3-propandiol, 1,2-propandiol, cyclohexanol, acetonitrile, propionitrile, acetone, butanone (methyl ethyl ketone), pentan-2-one (methyl propyl ketone), pentan-3-one (diethylketone), 4-methyl-2-pentanone (isobutyl-methyl-ketone), 3-methyl-butan-2-one (iso-propyl-methyl-ketone), 3,3-dimethyl-2-butanone (tert-butyl-methyl-ketone), cyclohexanone, methylacetate, ethylacetate, isopropylacetate, N-butylacetate, isobutylacetate, diethylcarbonate, 2-butoxyethylacetate, dioxane, THF, diethylether, 2-methyl-THF, methyl-tert-butylether, dimethylformamide, dimethylacetamide, dimethylsulfoxide (DMSO), nitromethane, and nitroethane.

Modification II can also be crystallized by effecting the crystallization by cooling concentrated solutions of the corresponding solvent. In a cooling crystallization the crystallization begin needs to be within the aforesaid temperature ranges. Parameters effecting the nucleation temperature and beginning of crystallization are concentration, cooling rate and time of adding possible seeding crystals of the wanted modification to a supersaturated solution. The concentration depends naturally of the solubility of fipronil in the corresponding solvent. The cooling rate is typically in between 5 K/h and 20 K/h. The cooling rate may not exceed 1 K/minute.

A person skilled in the art is able to perform a cooling crystallization in a corresponding solvent so that these conditions are met.

If the crystallization is not affected in a way that the nucleation begins in the aforesaid narrow temperature ranges, other modifications or mixtures of modifications result.

Modification II can be obtained from a solution in THF, or DCE by evaporation at from 40° C. to the boiling point of the solvent used. Evaporation from a THF solution at 20-25° C. yield a mixture of modifications I and II.

Alternatively modification II is obtainable from a solution in acetonitrile by cooling crystallization from 80 to 5° C. (cf. example 4).

In a further embodiment of the invention modification II is obtainable from a solution in toluene by a cooling crystallization when nucleation and crystallization starts above 90° C. (cf. example 5). In between 90 and 75° C. mixtures of II and III (F-ST) result.

In a further embodiment of the invention modification II is obtainable from a solution in monochlorobenzene (MCB) also in a cooling crystallization (cf. example 6).

In a further embodiment of the invention modification II is obtainable from a solution in mesitylene (cf. example 7).

In a further embodiment of the invention modification II is obtainable from a solution in dichlorobenzene (DCB) in two concentrations.

In a further embodiment of the invention modification II is obtainable from a solution in nitrobenzene (cf. example 8).

In a further embodiment of the invention modification II is obtainable from a solution in ethyl benzene when crystallization took place above 100° C. (cf. example 9). Preferably solutions with a fipronil content of 10 w.-% or more, more preferably of 15 w.-% or more are used.

In a further embodiment of the invention modification II is obtainable from a solution in CF₃-benzene at 90° C. or more, preferably 95° C. or above.

A detailed description of these steps is as follows:

Step i)

Suitable fipronil forms different from the crystalline modification II used in step i) are, for example, selected from amorphous fipronil or crystalline fipronil such as other triclinic or monoclinic forms, e.g. monoclinic fipronil of the space group C2/c, and also mixtures of crystalline modifications of fipronil.

The fipronil form used as starting material in step i) preferably has a purity of at least 85% by weight, in particular at least 90% by weight and especially at least 95% by weight. “Purity” means the absence of chemical compounds other than fipronil.

The solvent S used in step i) consists of either acetonitrile, DCB, DCE, ethyl benzene, MCB, mesitylene, nitrobenzene, THF, toluene, or CF₃-benzene, each pure or in combination with a polar solvent P.

In a preferred embodiment, the solvent S used in step i) consists of DCB, mesitylene, and nitrobenzene, each pure or in combination with a polar solvent P

In another preferred embodiment, the solvent S used in step i) consists of ethyl benzene, MCB, and toluene, each pure or in combination with a polar solvent P In step i), the fipronil form different from the crystalline modification II will usually be incorporated into the solvent S as a solid with mixing at a concentration and temperature where the solvent S is capable of completely dissolving the fipronil form.

The amount of fipronil form dissolved in the solvent S depends, on the nature of the solvent S and on the dissolution temperature. The person skilled in the art will be able to determine suitable conditions by standard experiments.

Step ii)

In step ii) of the process of this invention, fipronil is then crystallized. Crystallization can be effected in a customary manner, for example by cooling the solution obtained in step i), by adding a solvent which reduces the solubility, or by concentrating the solution, or by a combination of the measures mentioned above.

In a preferred embodiment, step ii) is carried out in the presence of seed crystals of the crystalline modification II.

To achieve a conversion into the crystalline modification II which is as complete as possible, the crystallization is carried out over a period (duration of crystallization) of at least 1 h, in particular at least 3 h. Duration of crystallization is understood by the person skilled in the art as meaning the period of time between the beginning of the measure which initiates crystallization and the isolation of the fipronil by separating the crystalline material from the mother liquor.

In general, the crystallization is allowed to proceed to a point where at least 60%, preferably at least 70%, in particular at least 90% by weight, for example from 80 to 90% by weight, of the fipronil employed has crystallized out.

Concentration of the solution is effected by gradually removing the solvent S, such as by evaporation in vacuo, either at low temperature or at about 20° C. to 25° C. or at elevated temperature, and/or in the presence of a flow of an inert gas such as nitrogen or argon. The values of “low temperature” and “elevated temperature” depend, on the nature of the solvent S, however should not exceed 60° C.

In a preferred embodiment, the crystallization is effected by concentrating the solution.

Step iii)

In step iii) of the process of this invention, the crystalline modification II is isolated using customary techniques for separating solid components from liquids, for example by filtration, centrifugation or decanting. In general, the isolated precipitate will be washed, for example with the solvent S used for the crystallization. The washing can be carried out in one or more steps. The washing is typically carried out at temperatures lower than 30° C. and in particular lower than 25° C., to keep the loss of the product of value as low as possible. The resulting crystalline fipronil or modification II can then be dried and subjected to further processing.

The preparation process consisting of steps i) to step iii) can be repeated in order to achieve higher purities of fipronil.

The crystalline modification II is especially suitable for efficiently combating the following pests:

-   millipedes (Diplopoda) such as Blaniulus or Narceus ssp; -   insects (Insecta) such as: -   ants, bees, wasps, sawflies (Hymenoptera), e.g. Atta capiguara, Atta     cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana,     Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea,     Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta,     Solenopsis richteri, Solenopsis xyloni, Pheidole megacephala,     Pogonomyrmex species such as Pogonomyrmex barbatus and Pogonomyrmex     californicus, Dasymutilla occidentalis, Bombus spp. Vespula     squamosa, Paravespula vulgaris, Paravespula pennsylvanica,     Paravespula germanica, Dolichovespula maculata, Vespa crabro,     Polistes rubiginosa, Camponotus floridanus, and Linepithema humile, -   beetles (Coleoptera), such as Agrilus sinuatus, Agriotes lineatus,     Agriotes obscurus and other Agriotes species, Amphimallus     solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus     pomorum, Aracanthus morei, Atomaria linearis, Blapstinus species,     Blastophagus piniperda, Blitophaga undata, Bothynoderes     punciventris, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis,     Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata,     Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema     tibialis, Conoderus vespertinus and other Conoderus species,     Conorhynchus mendicus, Crioceris asparagi, Cylindrocopturus     adspersus, Diabrotica (longicornis) barberi, Diabrotica     semi-punctata, Diabrotica speciosa, Diabrotica undecimpunctata,     Diabrotica virgifera and other Diabrotica species, Eleodes species,     Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus     brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera     postica, Ips typographus, Lema bilineata, Lema melanopus,     Leptinotarsa decemlineata, Limonius californicus and other Limonius     species, Lissorhoptrus oryzophilus, Listronotus bonariensis,     Melanotus communis and other Melanotus species, Meligethes aeneus,     Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,     Ortiorrhynchus sulcatus, Oryzophagus oryzae, Otiorrhynchus ovatus,     Oulema oryzae, Phaedon cochleariae, Phyllotreta chrysocephala,     Phyllophaga cuyabana and other Phyllophaga species, Phyllopertha     horticola, Phyllotreta nemorum, Phyllotreta striolata, and other     Phyllotreta species, Popillia japonica, Promecops carinicollis,     Premnotrypes voraz, Psylliodes species, Sitona lineatus, Sitophilus     granaria, Sternechus pinguis, Sternechus subsignatus, and Tanymechus     palliatus and other Tanymechus species, -   Centipedes (Chilopoda), e.g. Scutigera coleoptrata, -   Cockroaches (Blattaria-Blattodea), e.g. Blattella germanica,     Blattella asahinae, Periplaneta americana, Periplaneta japonica,     Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta     australasiae, and Blatta orientalis, -   Crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica,     Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus,     Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus     sanguinipes, Melanoplus spretus, Nomadacris septemfasciata,     Schistocerca americana, Schistocerca gregaria, Dociostaurus     maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus     variegatus, Hieroglyphus daganensis, Kraussaria angulifera,     Calliptamus italicus, Chortoicetes terminifera, and Locustana     pardalina, -   fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides     canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and     Nosopsyllus fasciatus, -   Flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus,     Aedes vexans, Agromyza oryzea, Anastrepha ludens, Anopheles     maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles     gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles     minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya     bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops     discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia     hominivorax, Contarinia sorghicola, Cordylobia anthropophaga,     Culicoides furens, Culex pipiens, Culex nigripalpus, Culex     quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta     melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia     antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia     hominis, Fannia canicularis, Gasterophilus intestinalis, Geomyza     Tripunctata, Glossina morsitans, Glossina palpalis, Glossina     fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis     equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens,     Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia     cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp.,     Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus     ovis, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya     hysocyami, Phlebotomus argentipes, Phorbia antiqua, Phorbia     brassicae, Phorbia coarctata, Progonya leyoscianii, Psila rosae,     Psorophora columbiae, Psorophora discolor, Prosimulium mixtum,     Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis,     Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus     bovinus, Tabanus atratus, Tabanus lineola, Tabanus similis, Tetanops     myopaeformis, Tipula olerace, and Tipula paludosa, -   Heteropterans (Heteroptera), such as Acrosternum hilare, Blissus     leucopterus, Cicadellidae such as Empoasca fabae, Chrysomelidae,     Cyrtopeltis notatus, Delpahcidae, Dysdercus cingulatus, Dysdercus     intermedius, Eurygaster integriceps, Euschistus impictiventris,     Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis,     Nephotettix species, Nezara viridula, Pentatomidae, Piesma quadrata,     Solubea insularis and Thyanta perditor, -   Aphids and other homopterans (Homoptera), e.g. Acyrthosiphon     onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis     forbesi, Aphis glycines, Aphis gossypii, Aphis grossulariae, Aphis     pomi, Aphis schneideri, Aphis spiraecola, Aphis sambuci,     Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui,     Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus     prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha     gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia     nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum     pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae,     Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae,     Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae,     Melanaphis pyrarius, Metopolophium dirhodum, Myzodes(Myzus)     persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia     ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Pemphigus     populivenae, and other Pemphigus species, Perkinsiella saccharicida,     Phorodon humuli, Psyllidae such as Psylla mali, Psylla piri and     other Psylla species, Rhopalomyzus ascalonicus, Rhopalosiphum     maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala,     Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa,     Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand,     and Viteus vitifolii, -   Lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis     segetum and other Agrotis species, Alabama argillacea, Anticarsia     gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus     piniarius, Cacoecia murinana, Capua reticulana, Chematobia brumata,     Chilo suppresalis and other Chilo species, Choristoneura fumiferana,     Choristoneura occidentalis, Cirphis unipuncta, Cnaphlocrocis     medinalis, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis,     Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus,     Eupoecilia ambiguella, Euxoa species, Evetria bouliana, Feltia     subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha     molesta, Heliothis armigera, Heliothis virescens, Heliothis zea,     Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta     malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma     exigua, Lerodea eufala, Leucoptera coffeella, Leucoptera scitella,     Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,     Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma     neustria, Mamestra brassicae, Momphidae, Orgyia pseudotsugata,     Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella,     Peridroma saucia, Phalera bucephala, Phthorimaea operculella,     Phyllocnistis citrella, Pieris brassicae, Plathypena scabra,     Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana,     Scrobipalpula absoluta, Sesamia nonagrioides and other Sesamia     species, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera     frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea     pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera     canadensis, -   lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus     humanus corporis, Pthirus pubis, Haematopinus eurysternus,     Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon     gallinae, Menacanthus stramineus and Solenopotes capillatus, -   orthopterans (Orthoptera), such as Acrididae, Acheta domestica,     Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria,     Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus,     Melanoplus sanguinipes, Melanoplus spretus, Nomadacris     septemfasciata, Schistocerca americana, Schistocerca peregrina,     Stauronotus maroccanus and Tachycines asynamorus, -   silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and     Thermobia domestica, -   termites (Isoptera), such as Calotermes flavicollis, Coptotermes     ssp., Dalbulus maidis, Heterotermes aureus, Leucotermes flavipes,     Macrotermes gilvus, Reticulitermes ssp., Termes natalensis,     Coptotermes formosanus, -   thrips (Thysanoptera), such as Frankliniella fusca, Frankliniella     occidentalis, Frankliniella tritici and other Frankliniella species,     Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips simplex, and     Thrips tabaci, -   ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g.     Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus,     Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor     variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus     hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata),     e.g. Ornithonyssus bacoti and Dermanyssus gallinae, -   true bugs (Hemiptera), e.g. Cimex lectularius, Cimex hemipterus,     Reduvius senilis, Triatoma spp., Rhodnius prolixus, and Arilus     critatus, -   Arachnoidea, such as arachnids (Acarina), for example of the     families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma     americanum, Amblyomma variegatum, Argas persicus, Boophilus     annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor     silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus,     Latrodectus mactans, Loxosceles reclusa, Ornithodorus moubata,     Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus     appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and     Eriophyidae species such as Aculus schlechtendali, Phyllocoptrata     oleivora and Eriophyes sheldoni; Tarsonemidae species such as     Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae     species such as Brevipalpus phoenicis; Tetranychidae species such as     Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus     pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus     ulmi, Panonychus citri, and Oligonychus pratensis, -   Earwigs (Dermaptera), e.g. forficula auricularia; and -   Nematodes, including plant parasitic nematodes and nematodes living     in the soil. Plant parasitic nematodes include, such as root knot     nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne     javanica, and other Meloidogyne species; cyst-forming nematodes,     Globodera rostochiensis and other Globodera species; Heterodera     avenae, Heterodera glycines, Heterodera schachtii, Heterodera     trifolii, and other Heterodera species; Seed gall nematodes, Anguina     species; Stem and foliar nematodes, Aphelenchoides species; Sting     nematodes, Belonolaimus longicaudatus and other Belonolaimus     species; Pine nematodes, Bursaphelenchus xylophilus and other     Bursaphelenchus species; Ring nematodes, Criconema species,     Criconemella species, Criconemoides species, Mesocriconema species;     Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci     and other Ditylenchus species; Awl nematodes, Dolichodorus species;     Spiral nematodes, Heliocotylenchus multicinctus and other     Helicotylenchus species; Sheath and sheathoid nematodes,     Hemicycliophora species and Hemicriconemoides species;     Hirshmanniella species; Lance nematodes, Hoploaimus species; false     rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus     elongatus and other Longidorus species; Pin nematodes, Paratylenchus     species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus     penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other     Pratylenchus species; Burrowing nematodes, Radopholus similis and     other Radopholus species; Reniform nematodes, Rotylenchus robustus     and other Rotylenchus species; Scutellonema species; Stubby root     nematodes, Trichodorus primitivus and other Trichodorus species,     Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni,     Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus     nematodes, Tylenchulus species, Dagger nematodes, Xiphinema species     and other plant parasitic nematode species.

Moreover, the crystalline modification II is especially useful for the control of crop pests, in particular of the Coleoptera, Lepidoptera and Acarina orders.

Moreover, the crystalline modification II is especially useful for the control of non-crop pests (household, turf, ornamental). Non-crop pests are pests of the classes Chilopoda and Diplopoda and of the orders Isoptera, Diptera, Blattaria (Blattodea), Dermaptera, Hemiptera, Hymenoptera, Orthoptera, Siphonaptera, Thysanura, Phthiraptera, and Acarina.

For use according to the present invention, the crystalline modification II can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.

The formulations are prepared in a known manner (see e.g. for review U.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, U.S. Pat. Nos. 4,172,714, 4,144,050, 3,920,442, 5,180,587, 5,232,701, 5,208,030, GB 2,095,558, U.S. Pat. No. 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001, 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired surfactants (e.g. adjuvans, emulsifiers, dispersing agents), preservatives, antifoaming agents, anti-freezing agents, for seed treatment formulations also optionally colorants and/or binders and/or gelling agents.

Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.

Examples of suitable carriers are ground natural minerals (for example kaolins, clays, talc, chalk) and ground synthetic minerals (for example highly disperse silica, silicates). Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.

Suitable preservatives are for example Dichlorophen and enzylalkoholhemiformal.

Seed Treatment formulations may additionally comprise binders and optionally colorants.

Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tylose and copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Examples of a gelling agent is carrageen (Satiagel®).

Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.

Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s). In this case, the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).

For seed treatment purposes, the respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.

The crystalline modification II can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1% per weight.

The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.

The following are examples of formulations: 1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.

A) Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formulation with 10% (w/w) of active compound(s) is obtained.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compound(s) are dissolved in 80 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)

75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s), whereby a formulation with 75% (w/w) of active compound(s) is obtained.

H) Gel-Formulation (GF) (for Seed Treatment Purposes Only)

In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent/wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.

2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted.

I) Dustable Powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound(s) is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound(s) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.

K) ULV Solutions (UL)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulation can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds.

In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.

The invention relates in particular to pesticidal or parasiticidal compositions in the form of an aqueous suspension concentrate (SC). Such suspension concentrates comprise the crystalline modification II in a finely divided particulate form, where the particles of the crystalline modification II are suspended in an aqueous medium. The size of the active compound particles, i.e. the size which is not exceeded by 90% by weight of the active compound particles, is typically below 30 μm, in particular below 20 μm. Advantageously, at least 40% by weight and in particular at least 60% by weight of the particles in the SCs according to the invention have diameters below 2 μm.

In addition to the active compound, suspension concentrates typically comprise surfactants, and also, if appropriate, antifoam agents, thickeners, antifreeze agents, stabilizers (biocides), agents for adjusting the pH and anticaking agents.

In such SCs, the amount of active compound, i.e. the total amount of the crystalline modification II and, if appropriate, further active compounds is usually in the range from 10 to 70% by weight, in particular in the range from 20 to 50% by weight, based on the total weight of the suspension concentrate.

Preferred surfactants are anionic and nonionic surfactants. The amount of surfactants will generally be from 0.5 to 20% by weight, in particular from 1 to 15% by weight and particularly preferably from 1 to 10% by weight, based on the total weight of the SCs according to the invention. Preferably, the surfactants comprise at least one anionic surfactant and at least one nonionic surfactant, the ratio of anionic to nonionic surfactant typically being in the range from 10:1 to 1:10.

Examples of anionic surfactants include alkylaryl sulfonates, phenyl sulfonates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyaryl phenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates, paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fatty acids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, alkyl phosphates, alkylaryl phosphates, for example tristyryl phosphates, and also polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above. Preferred anionic surfactants are those which carry at least one sulfonate group, and in particular their alkali metal and their ammonium salts.

Examples of nonionic surfactants comprise alkylphenol alkoxylates, alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isotridecyl alcohol, fatty amides, methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fatty acid esters, polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers (polyethylene oxide/polypropylene oxide block copolymers) and mixtures thereof. Preferred nonionic surfactants are fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates, fatty acid polyglycol esters and ethylene oxide/propylene oxide block copolymers and mixtures thereof.

In particular, the SCs according to the invention comprise at least one surfactant which improves wetting of the plant parts by the aqueous application form (wetting agent) and at least one surfactant which stabilizes the dispersion of the active compound particles in the SC (dispersant). The amount of wetting agent is typically in the range from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight and especially from 0.5 to 3% by weight, based on the total weight of the SC. The amount of dispersant is typically from 0.5 to 10% by weight and in particular from 0.5 to 5% by weight, based on the total weight of the SC.

Preferred wetting agents are of anionic or nonionic nature and selected, for example, from naphthalenesulfonic acids including their alkali metal, alkaline earth metal, ammonium and amine salts, furthermore fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycol esters.

Preferred dispersants are of anionic or nonionic nature and selected, for example, from polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers, alkylaryl phosphates, for example tristyryl phosphates, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above.

Viscosity-modifying additives (thickeners) suitable for the SCs according to the invention are in particular compounds which bestow upon the formulation pseudoplastic flow properties, i.e. high viscosity in the resting state and low viscosity in the agitated state. Suitable are, in principle, all compounds used for this purpose in suspension concentrates. Mention may be made, for example, of inorganic substances, such as bentonites or attapulgites (for example Attaclay® from Engelhardt), and organic substances, such as polysaccharides and heteropolysaccharides, such as xanthan gum such as sold under the trademarks Kelzan® from Kelco, Rhodopol® 23 from Rhone Poulenc or Veegum® from R.T. Vanderbilt, and preference is given to using xanthan gum. Frequently, the amount of viscosity-modifying additives is from 0.1 to 5% by weight, based on the total weight of the SC.

Antifoam agents suitable for the SCs according to the invention are, for example, silicone emulsions known for this purpose (Silikon® SRE, from Wacker, or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, defoamers of the type of aqueous wax dispersions, solid defoamers (so-called Compounds), organofluorine compounds and mixtures thereof. The amount of antifoam agent is typically from 0.1 to 1% by weight, based on the total weight of the SC.

Bactericides may be added for stabilizing the suspension concentrates according to the invention. Suitable bactericides are those based on isothiazolones, for example Proxel® from ICI or Acticide® RS from Thor Chemie or Kathon® MK from Rohm & Haas. The amount of bactericides is typically from 0.05 to 0.5% by weight, based on the total weight of the SC.

Suitable antifreeze agents are liquid polyols, for example ethylene glycol, propylene glycol or glycerol. The amount of antifreeze agents is generally from 1 to 20% by weight, in particular from 5 to 10% by weight, based on the total weight of the suspension concentrate.

If appropriate, the SCs according to the invention may comprise buffers for regulating the pH. Examples of buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boric acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.

The invention relates in particular to pesticidal or parasiticidal compositions in the form of water-dispersible granules (WG) or a water dispersible powder (WP). Such formulations comprise the crystalline modification II in a finely divided particulate form, where the particles of the crystalline modification II are homogenized in a solid or powder form. The size of the active compound particles, i.e. the size which is not exceeded by 90% by weight of the active compound particles, is typically below 30 μm, in particular below 20 μm. Advantageously, at least 40% by weight and in particular at least 60% by weight of the particles in the WGs or WPs according to the invention have diameters below 5 μm.

In addition to the active compound, water-dispersible powders and water dispersible granules typically comprise surfactants, and also, if appropriate, antifoam agents, fillers, binders, and anticaking agents.

In such WGs and WPs, the amount of active compound, i.e. the total amount of the crystalline modification II and, if appropriate, further active compounds is usually in the range from 10 to 90% by weight, in particular in the range from 20 to 75% by weight, based on the total weight of the WG/WP.

Preferred surfactants are anionic and nonionic surfactants. The amount of surfactants will generally be from 0.5 to 20% by weight, in particular from 1 to 15% by weight and particularly preferably from 1 to 10% by weight, based on the total weight of the WGs or WPs according to the invention. Preferably, the surfactants comprise at least one anionic surfactant and at least one nonionic surfactant, the ratio of anionic to nonionic surfactant typically being in the range from 10:1 to 1:10.

Examples of anionic surfactants include alkylaryl sulfonates, phenyl sulfonates, alkyl sulfates, alkyl sulfonates, alkyl ether sulfates, alkylaryl ether sulfates, alkyl polyglycol ether phosphates, polyaryl phenyl ether phosphates, alkyl sulfosuccinates, olefin sulfonates, paraffin sulfonates, petroleum sulfonates, taurides, sarcosides, fatty acids, alkylnaphthalenesulfonic acids, naphthalenesulfonic acids, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenolsulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, alkyl phosphates, alkylaryl phosphates, for example tristyryl phosphates, and also polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above. Preferred anionic surfactants are those which carry at least one sulfonate group, and in particular their alkali metal and their ammonium salts.

Examples of nonionic surfactants comprise alkylphenol alkoxylates, alcohol alkoxylates, fatty amine alkoxylates, polyoxyethylene glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates, fatty acid polyglycol esters, isotridecyl alcohol, fatty amides, methylcellulose, fatty acid esters, alkyl polyglycosides, glycerol fatty acid esters, polyethylene glycol, polypropylene glycol, polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers (polyethylene oxide/polypropylene oxide block copolymers) and mixtures thereof. Preferred nonionic surfactants are fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, lanolin ethoxylates, fatty acid polyglycol esters and ethylene oxide/propylene oxide block copolymers and mixtures thereof.

In particular, the WGs or WPs according to the invention comprise at least one surfactant which improves wetting of the formulation by the aqueous application form (wetting agent) and at least one surfactant which allows dispersion of the active compound particles in aqueous dilutions. The amount of wetting agent is typically in the range from 0.5 to 10% by weight, in particular from 0.5 to 5% by weight and especially from 0.5 to 3% by weight, based on the total weight of the WG/WP. The amount of dispersant is typically from 0.5 to 10% by weight and in particular from 2.0 to 8% by weight, based on the total weight of the WG/WP.

Preferred wetting agents are of anionic or nonionic nature and selected, for example, from naphthalenesulfonic acids including their alkali metal, alkaline earth metal, ammonium and amine salts, furthermore fatty alcohol ethoxylates, alkyl polyglycosides, glycerol fatty acid esters, castor oil alkoxylates, fatty acid alkoxylates, fatty amide alkoxylates, fatty polydiethanolamides, lanolin ethoxylates and fatty acid polyglycol esters.

Preferred dispersants are of anionic or nonionic nature and selected, for example, from polyethylene glycol/polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polypropylene glycol alkyl ethers, polyethylene glycol/polypropylene glycol ether block copolymers, alkylaryl phosphates, for example tristyryl phosphates, sodium phosphates, sodium lauryl sulphate, modified cellulose gum, polyvinylpyrrolidinone, lignosulfonic acids, condensates of sulfonated naphthalenes with formaldehyde or with formaldehyde and phenol and, if appropriate, urea, and also condensates of phenol-sulfonic acid, formaldehyde and urea, lignosulfite waste liquors and lignosulfonates, polycarboxylates, such as, for example, polyacrylates, maleic anhydride/olefin copolymers (for example Sokalan® CP9, BASF), including the alkali metal, alkaline earth metal, ammonium and amine salts of the substances mentioned above.

Antifoam agents suitable for the WGs or WPs according to the invention are, for example, tallow soap known for this purpose (Agnique Soap L, Foamaster Soap L), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. The amount of antifoam agent is typically from 0.1 to 1% by weight, based on the total weight of the WG/WP.

Fillers, binders, or additional dispersing aids suitable for the WGs and WPs according to the invention typically make up the remainder of the formulation. These typically are for example kaolin or attapulgite clay, fumed or precipitated silica, diatomaceous earth, ammonium sulphate, or calcium silicate.

The crystalline modification II is effective through both contact and ingestion.

According to a preferred embodiment of the invention, the crystalline modification II is employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.

According to another preferred embodiment of the invention, for use against non-crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the crystalline modification II is prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickiness, moisture retention or aging characteristics. The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and/or sex pheromones. Suitable feeding stimulants are chosen, for example, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, crickets powder, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey, or from salts such as ammonium sulfate, ammonium carbonate or ammonium acetate. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.

Compositions of this invention may also contain other active ingredients, for example other pesticides, insecticides, fungicides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

The following list of pesticidal or parasiticidal compounds which can be used together with the crystalline modification II according to the invention is intended to illustrate the possible combinations, but not to impose any limitation:

-   A.1. Organo(thio)phosphates: acephate, azamethiphos,     azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos,     diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion,     fenitrothion, fenthion, isoxathion, malathion, methamidophos,     methidathion, methyl-parathion, mevinphos, monocrotophos,     oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone,     phosmet, phosphamidon, phorate, phoxim, pirimiphos-methyl,     profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos,     triazophos, trichlorfon; -   A.2. Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb,     carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb,     methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb,     triazamate; -   A.3. Pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,     cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin,     zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox,     fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin,     permethrin, prallethrin, pyrethrin I and II, resmethrin,     silafluofen, tau-fluvalinate, tefluthrin, tetramethrin,     tralomethrin, transfluthrin, profluthrin, dimefluthrin; -   A.4. Growth regulators: a) chitin synthesis inhibitors:     benzoylureas: chlorfluazuron, diflubenzuron, flucycloxuron,     flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron,     triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole,     clofentazine; b) ecdysone antagonists: halofenozide,     methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids:     pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis     inhibitors: spirodiclofen, spiromesifen, spirotetramat; -   A.5. Nicotinic receptor agonists/antagonists compounds:     clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram,     acetamiprid, thiacloprid; the thiazol compound of formula Γ¹

-   A.6. GABA antagonist compounds: acetoprole, endosulfan, ethiprole,     fipronil, vaniliprole, pyrafluprole, pyriprole,     5-Amino-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-trifluoromethanesulfonyl-1H-pyrazole-3-carbothioic     acid amide of formula Γ²

-   A.7. Macrocyclic lactone insecticides: abamectin, emamectin,     milbemectin, lepimectin, spinosad; -   A.8. METI I compounds: fenazaquin, pyridaben, tebufenpyrad,     tolfenpyrad, flufenerim; -   A.9. METI Hand III compounds: acequinocyl, fluacyprim,     hydramethylnon; -   A.10. Uncoupler compounds: chlorfenapyr; -   A.11. Oxidative phosphorylation inhibitor compounds: cyhexatin,     diafenthiuron, fenbutatin oxide, propargite; -   A.12. Moulting disrupter compounds: cyromazine; -   A.13. Mixed Function Oxidase inhibitor compounds: piperonyl     butoxide; -   A.14. Sodium channel blocker compounds: indoxacarb, metaflumizone, -   A.15. Various: benclothiaz, bifenazate, cartap, flonicamid,     pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide,     cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, -   the anthranilamide compounds of formula Γ³

wherein A¹ is CH₃, Cl, Br, I, X is C—H, C—Cl, C—F or N, Y′ is F, Cl, or Br, Y″ is hydrogen, F, Cl, CF₃, B¹ is hydrogen, Cl, Br, I, CN, B² is Cl, Br, CF₃, OCH₂CF₃, OCF₂H, and R^(B) is hydrogen, CH₃ or CH(CH₃)₂, and the malononitrile compounds as described in JP 2002 284608, WO 02/89579, WO 02/90320, WO 02/90321, WO 04/06677, WO 04/20399, JP 2004 99597, WO 05/68423, WO 05/68432, or WO 05/63694, especially the malononitrile compounds CF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H (2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F (2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃(2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile) and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile).

The commercially available compounds of the group A may be found in The Pesticide Manual, 13^(th) Edition, British Crop Protection Council (2003) among other publications. Thioamides of formula Γ² and their preparation have been described in WO 98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Benclothiaz and its preparation have been described in EP-A1 454621. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p. 237-243 and in U.S. Pat. No. 4,822,779. Pyrafluprole and its preparation have been described in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in U.S. Pat. No. 6,335,357. Amidoflumet and its preparation have been described in U.S. Pat. No. 6,221,890 and in JP 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. Cyflumetofen and its preparation have been described in WO 04/080180. Anthranilamides of formula Γ³ and their preparation have been described in WO 01/70671; WO 02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO 04/33468; and WO 05/118552. The malononitrile compounds CF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H (2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F (2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile), CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃(2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile), CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile) and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H (2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile) have been described in WO 05/63694.

The following list of fungicidal compounds which can be used together with the crystalline modification II according to the invention is intended to illustrate the possible combinations, but not to impose any limitation:

Preferred are the binary mixtures containing modification II as compound I.

Preferred are the tertiary mixtures containing modification II as compound I, a compound IIA, and a compound IIB.

Preferred are the quaternary mixtures containing modification II as compound I, a compound IIA, and two compounds IIB1 and IIB2, resp.

Especially preferred are binary mixtures containing modification II as compound I and a fungicidal compound IIA selected from the list comprising azoles: cyproconazole, di-fenoconazole, epoxiconazole, fenbuconazole, fluquinconazole, flutriafol, hexaconazole, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole, tetraconazole, triadimenol, triadimefon, triticonazole, cyazofamid, imazalil, prochloraz, triflumizol, benomyl, carbendazim, thiabendazole, ethaboxam, and hymexazole.

Especially preferred are binary mixtures containing modification II as compound I and a fungicidal compound IIA selected from the list comprising strobilurins: azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, methyl (2-chloro-5-[1-(3-methylbenzyloxy-imino)ethyl]benzyl)carbamate, methyl (2-chloro-5-[1-(6-methylpyridin-2-ylmethoxy-imino)ethyl]benzyl)carbamate, and methyl 2-(ortho-((2,5-dimethylphenyloxy-methylene)phenyl)-3-methoxyacrylate;

Especially preferred are binary mixtures containing modification II as compound I and a fungicidal compound IIA selected from the list comprising carboxamides: boscalid, carboxin, benalaxyl, fenhexamid, flutolanil, furametpyr, metalaxyl, mefenoxam (metalaxyl-M), ofurace, oxadixyl, oxycarboxin, penthiopyrad, thifluzamide, tiadinil, dimethomorph, fluopicolide (picobenzamid), diclocymet, N-(4′-bromobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-trifluoromethylbiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(4′-chloro-3′-fluorobiphenyl-2-yl)-4-difluoromethyl-2-methylthiazole-5-carboxamide, N-(3′,4′-dichloro-4-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide; 3,4-dichloro-N-(2-cyanophenyl)isothiazol-5-carboxamide; N-(2′,4′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,4′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,4′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′,4′-dichloro-biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′,5′-difluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(3′,5′-difluoro-biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(3′,5′-dichlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide, N-(3′,5′-difluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(3′,5′-dichlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(3′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide, N-(3′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(3′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(3′-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′-fluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(2′-chlorobiphenyl-2-yl)-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide; N-(2′-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′-chlorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(2′-fluoro-4′-chloro-5′-methylbiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-(3′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide; N-(2′,4′,5′-trifluorobiphenyl-2-yl)-1-methyl-3-difluoromethyl-1H-pyrazole-4-carboxamide; N-(3′,4′,5′-tri-fluorobiphenyl-2-yl)-3-chlorofluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-[2-(1,1,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide; N-[2-(1,1,2,3,3,3-hexafluor-opropoxy)-phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-[2-(2-chloro-1,1,2-trifluoroethoxy)phenyl]-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; N-[2-(2-chlor-1,1,2-trifluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-[2-(1,1,2,2-tetra-fluoroethoxy)phenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carbox-amide; N-[2-(1,1,2,2-tetrafluoro-ethoxy)phenyl]-1-methyl-3-trifluoro-methyl-1H-pyrazole-4-carboxamide; N-(4′-(trifluoro-methylthio)biphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; N-(4′-(trifluoromethyl-thio)biphenyl-2-yl)-1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide; and 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid [2-(1,2-dimethyl-propyl)-phenyl]-amide.

Especially preferred are binary mixtures containing modification II as compound I and a fungicidal compound IIA selected from the list comprising heterocylic compounds: pyrimethanil, fenpiclonil, fludioxonil, aldimorph, dodemorph, fenpropimorph, tridemorph, iprodione, procymidone, famoxadone, fenamidone, octhilinone, probenazole, diclomezine, pyroquilon, proquinazid, tricyclazole, captafol, captan, dazomet, fenoxanil, quinoxyfen, 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine, 6-(3,4-dichloro-phenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 6-(4-tert-butylphenyl)-5-methyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-methyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-methyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 6-methyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 6-ethyl-5-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 5-ethyl-6-(3,5,5-trimethyl-hex-yl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine, 6-octyl-5-propyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine, 5-methoxymethyl-6-octyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine, 6-octyl-5-trifluoromethyl-[1,2,4]tri-azolo[1,5-a]pyrimidine-7-ylamine, and 5-trifluoromethyl-6-(3,5,5-trimethyl-hexyl)-[1,2,4]triazolo[1,5-a]pyrimidine-7-ylamine.

Especially preferred are binary mixtures containing modification II as compound I and a fungicidal compound IIA selected from the list comprising carbamates: mancozeb, maneb, metam, metiram, ferbam, propineb, thiram, zineb, ziram; diethofencarb, iprovalicarb, propamocarb, and methyl 3-(4-chlorophenyl)-3-(2-isopropoxycarbonyl-amino-3-methylbutyrylamino)propanoate.

Especially preferred are binary mixtures containing modification II as compound I and a fungicidal compound IIA selected from the list comprising: guazatine; streptomycin, validamycin A; binapacryl, dinocap, dinobuton; dithianon, isoprothiolane; fentin salts, such as fentin-acetate; edifenphos, iprobenfos, fosetyl, pyrazophos, chlorothalonil, dichlofluanid, flusulfamide, phthalide, quintozene, thiophanate-methyl, tolylfluanid; copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl, metrafenone, and spiroxamine.

The active compounds IIA mentioned above, their preparation and their action against harmful fungi are generally known (cf: http://www.hclrss.demon.co.uk/index.html); they are commercially available. The compounds named according to IUPAC, their preparation and their fungicidal activity are likewise known from EP-A 12 01 648; EP-A 226 917; WO 98/46608; WO 99/24413; WO 2004/049804; WO 2003/066609; WO 2003/053145; WO 2003/14103; EP-A 10 35 122; EP-A 10 28 125; EP-A 71 792; EP-A 141 317; WO 2003/009687; WO 05/087771; WO 2005/087772; WO 2005/087773; WO 2006/087325; WO 2006/087325; WO 2006/092428; WO 2006/092428; WO 2006/087343; WO 2001/42223; WO 2005/34628; WO 2005/123689; WO 2005/123690; WO 2006/120219; PCT/EP2006/064991; WO 2007/017450, and EP Application No. 06123463.9

With respect to their intended use, the following tertiary and quaternary mixtures of modification II as compound I are especially preferred:

Table 1

Mixtures wherein compound IIA is trifloxystrobin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 2

Mixtures wherein compound IIA is azoxystrobin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 3

Mixtures wherein compound IIA is pyraclostrobin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 4

Mixtures wherein compound IIA is boscalid, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 5

Mixtures wherein compound IIA is metalaxyl, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 6

Mixtures wherein compound IIA is metalaxyl-M, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 7

Mixtures wherein compound IIA is cyproconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 8

Mixtures wherein compound IIA is epoxiconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 9

Mixtures wherein compound IIA is fenbuconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 10

Mixtures wherein compound IIA is fluquinconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 11

Mixtures wherein compound IIA is flutriafol, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 12

Mixtures wherein compound IIA is ipconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 13

Mixtures wherein compound IIA is metconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 14

Mixtures wherein compound IIA is propiconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 15

Mixtures wherein compound IIA is prothioconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 16

Mixtures wherein compound IIA is tebuconazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 17

Mixtures wherein compound IIA is triadimenol, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 18

Mixtures wherein compound IIA is triticonazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 19

Mixtures wherein compound IIA is imazalil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 20

Mixtures wherein compound IIA is prochloraz, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 21

Mixtures wherein compound IIA is carbendazim, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 22

Mixtures wherein compound IIA is thiabendazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 23

Mixtures wherein compound IIA is ethaboxam, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 24

Mixtures wherein compound IIA is hymexazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 25

Mixtures wherein compound IIA is pyrimethanil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 26

Mixtures wherein compound IIA is fludioxonil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 27

Mixtures wherein compound IIA is aldimorph, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 28

Mixtures wherein compound IIA is dodemorph, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 29

Mixtures wherein compound IIA is fenpropimorph, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 30

Mixtures wherein compound IIA is iprodione, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 31

Mixtures wherein compound IIA is captan, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 32

Mixtures wherein compound IIA is fenoxanil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 33

Mixtures wherein compound IIA is probenazole, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 34

Mixtures wherein compound IIA is mancozeb, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 35

Mixtures wherein compound IIA is metiram, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 36

Mixtures wherein compound IIA is thiram, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 37

Mixtures wherein compound IIA is ziram, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 38

Mixtures wherein compound IIA is guazatin, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 39

Mixtures wherein compound IIA is thiophanate-methyl, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 40

Mixtures wherein compound IIA is chlorothalonil, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

Table 41

Mixtures wherein compound IIA is metrafenone, and the combination of compounds IIB1 and IIB2 in each case corresponds to a row of Table Q.

TABLE Q Mixture No. Compound IIB1 Compound IIB2 M-1 azoxystrobin — M-2 azoxystrobin boscalid M-3 azoxystrobin metalaxyl M-4 azoxystrobin cyproconazole M-5 azoxystrobin epoxiconazole M-6 azoxystrobin fenbuconazole M-7 azoxystrobin fluquinconazole M-8 azoxystrobin flutriafol M-9 azoxystrobin ipconazole M-10 azoxystrobin metconazole M-11 azoxystrobin propiconazole M-12 azoxystrobin prothioconazole M-13 azoxystrobin tebuconazole M-14 azoxystrobin triadimenol M-15 azoxystrobin triticonazole M-16 azoxystrobin imazalil M-17 azoxystrobin prochloraz M-18 azoxystrobin carbendazim M-19 azoxystrobin thiabendazole M-20 azoxystrobin ethaboxam M-21 azoxystrobin hymexazole M-22 azoxystrobin pyrimethanil M-23 azoxystrobin fludioxonil M-24 azoxystrobin aldimorph M-25 azoxystrobin dodemorph M-26 azoxystrobin fenpropimorph M-27 azoxystrobin iprodione M-28 azoxystrobin captan M-29 azoxystrobin fenoxanil M-30 azoxystrobin probenazol M-31 azoxystrobin mancozeb M-32 azoxystrobin metiram M-33 azoxystrobin thiram M-34 azoxystrobin ziram M-35 azoxystrobin guazatin M-36 azoxystrobin thiophanate- methyl M-37 azoxystrobin chlorothalonil M-38 azoxystrobin metrafenone M-39 trifloxystrobin — M-40 trifloxystrobin boscalid M-41 trifloxystrobin metalaxyl M-42 trifloxystrobin cyproconazole M-43 trifloxystrobin epoxiconazole M-44 trifloxystrobin fenbuconazole M-45 trifloxystrobin fluquinconazole M-46 trifloxystrobin flutriafol M-47 trifloxystrobin ipconazole M-48 trifloxystrobin metconazole M-49 trifloxystrobin propiconazole M-50 trifloxystrobin prothioconazole M-51 trifloxystrobin tebuconazole M-52 trifloxystrobin triadimenol M-53 trifloxystrobin triticonazole M-54 trifloxystrobin imazalil M-55 trifloxystrobin prochloraz M-56 trifloxystrobin carbendazim M-57 trifloxystrobin thiabendazole M-58 trifloxystrobin ethaboxam M-59 trifloxystrobin hymexazole M-60 trifloxystrobin pyrimethanil M-61 trifloxystrobin fludioxonil M-62 trifloxystrobin aldimorph M-63 trifloxystrobin dodemorph M-64 trifloxystrobin fenpropimorph M-65 trifloxystrobin iprodione M-66 trifloxystrobin captan M-67 trifloxystrobin fenoxanil M-68 trifloxystrobin probenazol M-69 trifloxystrobin mancozeb M-70 trifloxystrobin metiram M-71 trifloxystrobin thiram M-72 trifloxystrobin ziram M-73 trifloxystrobin guazatin M-74 trifloxystrobin thiophanate- methyl M-75 trifloxystrobin chlorothalonil M-76 trifloxystrobin metrafenone M-77 orysastrobin — M-78 orysastrobin boscalid M-79 orysastrobin metalaxyl M-80 orysastrobin cyproconazole M-81 orysastrobin epoxiconazole M-82 orysastrobin fenbuconazole M-83 orysastrobin fluquinconazole M-84 orysastrobin flutriafol M-85 orysastrobin ipconazole M-86 orysastrobin metconazole M-87 orysastrobin propiconazole M-88 orysastrobin prothioconazole M-89 orysastrobin tebuconazole M-90 orysastrobin triadimenol M-91 orysastrobin triticonazole M-92 orysastrobin imazalil M-93 orysastrobin prochloraz M-94 orysastrobin carbendazim M-95 orysastrobin thiabendazole M-96 orysastrobin ethaboxam M-97 orysastrobin hymexazole M-98 orysastrobin pyrimethanil M-99 orysastrobin fludioxonil M-100 orysastrobin aldimorph M-101 orysastrobin dodemorph M-102 orysastrobin fenpropimorph M-103 orysastrobin iprodione M-104 orysastrobin captan M-105 orysastrobin fenoxanil M-106 orysastrobin probenazol M-107 orysastrobin mancozeb M-108 orysastrobin metiram M-109 orysastrobin thiram M-110 orysastrobin ziram M-111 orysastrobin guazatin M-112 orysastrobin thiophanate- methyl M-113 orysastrobin chlorothalonil M-114 orysastrobin metrafenone M-115 pyraclostrobin — M-116 pyraclostrobin boscalid M-117 pyraclostrobin metalaxyl M-118 pyraclostrobin cyproconazole M-119 pyraclostrobin epoxiconazole M-120 pyraclostrobin fenbuconazole M-121 pyraclostrobin fluquinconazole M-122 pyraclostrobin flutriafol M-123 pyraclostrobin ipconazole M-124 pyraclostrobin metconazole M-125 pyraclostrobin propiconazole M-126 pyraclostrobin prothioconazole M-127 pyraclostrobin tebuconazole M-128 pyraclostrobin triadimenol M-129 pyraclostrobin triticonazole M-130 pyraclostrobin imazalil M-131 pyraclostrobin prochloraz M-132 pyraclostrobin carbendazim M-133 pyraclostrobin thiabendazole M-134 pyraclostrobin ethaboxam M-135 pyraclostrobin hymexazole M-136 pyraclostrobin pyrimethanil M-137 pyraclostrobin fludioxonil M-138 pyraclostrobin aldimorph M-139 pyraclostrobin dodemorph M-140 pyraclostrobin fenpropimorph M-141 pyraclostrobin iprodione M-142 pyraclostrobin captan M-143 pyraclostrobin fenoxanil M-144 pyraclostrobin probenazol M-145 pyraclostrobin mancozeb M-146 pyraclostrobin metiram M-147 pyraclostrobin thiram M-148 pyraclostrobin ziram M-149 pyraclostrobin guazatin M-150 pyraclostrobin thiophanate- methyl M-151 pyraclostrobin chlorothalonil M-152 pyraclostrobin metrafenone M-153 boscalid — M-154 boscalid metalaxyl M-155 boscalid cyproconazole M-156 boscalid epoxiconazole M-157 boscalid fenbuconazole M-158 boscalid fluquinconazole M-159 boscalid flutriafol M-160 boscalid ipconazole M-161 boscalid metconazole M-162 boscalid propiconazole M-163 boscalid prothioconazole M-164 boscalid tebuconazole M-165 boscalid triadimenol M-166 boscalid triticonazole M-167 boscalid imazalil M-168 boscalid prochloraz M-169 boscalid carbendazim M-170 boscalid thiabendazole M-171 boscalid ethaboxam M-172 boscalid hymexazole M-173 boscalid pyrimethanil M-174 boscalid fludioxonil M-175 boscalid aldimorph M-176 boscalid dodemorph M-177 boscalid fenpropimorph M-178 boscalid iprodione M-179 boscalid captan M-180 boscalid fenoxanil M-181 boscalid probenazol M-182 boscalid mancozeb M-183 boscalid metiram M-184 boscalid thiram M-185 boscalid ziram M-186 boscalid guazatin M-187 boscalid thiophanate- methyl M-188 boscalid chlorothalonil M-189 boscalid metrafenone M-190 metalaxyl — M-191 metalaxyl cyproconazole M-192 metalaxyl epoxiconazole M-193 metalaxyl fenbuconazole M-194 metalaxyl fluquinconazole M-195 metalaxyl flutriafol M-196 metalaxyl ipconazole M-197 metalaxyl metconazole M-198 metalaxyl propiconazole M-199 metalaxyl prothioconazole M-200 metalaxyl tebuconazole M-201 metalaxyl triadimenol M-202 metalaxyl triticonazole M-203 metalaxyl imazalil M-204 metalaxyl prochloraz M-205 metalaxyl carbendazim M-206 metalaxyl thiabendazole M-207 metalaxyl ethaboxam M-208 metalaxyl hymexazole M-209 metalaxyl pyrimethanil M-210 metalaxyl fludioxonil M-211 metalaxyl aldimorph M-212 metalaxyl dodemorph M-213 metalaxyl fenpropimorph M-214 metalaxyl iprodione M-215 metalaxyl captan M-216 metalaxyl fenoxanil M-217 metalaxyl probenazol M-218 metalaxyl mancozeb M-219 metalaxyl metiram M-220 metalaxyl thiram M-221 metalaxyl ziram M-222 metalaxyl guazatin M-223 metalaxyl thiophanate- methyl M-224 metalaxyl chlorothalonil M-225 metalaxyl metrafenone M-226 cyproconazole — M-227 cyproconazole epoxiconazole M-228 cyproconazole fenbuconazole M-229 cyproconazole fluquinconazole M-230 cyproconazole flutriafol M-231 cyproconazole ipconazole M-232 cyproconazole metconazole M-233 cyproconazole propiconazole M-234 cyproconazole prothioconazole M-235 cyproconazole tebuconazole M-236 cyproconazole triadimenol M-237 cyproconazole triticonazole M-238 cyproconazole imazalil M-239 cyproconazole prochloraz M-240 cyproconazole carbendazim M-241 cyproconazole thiabendazole M-242 cyproconazole ethaboxam M-243 cyproconazole hymexazole M-244 cyproconazole pyrimethanil M-245 cyproconazole fludioxonil M-246 cyproconazole aldimorph M-247 cyproconazole dodemorph M-248 cyproconazole fenpropimorph M-249 cyproconazole iprodione M-250 cyproconazole captan M-251 cyproconazole fenoxanil M-252 cyproconazole probenazol M-253 cyproconazole mancozeb M-254 cyproconazole metiram M-255 cyproconazole thiram M-256 cyproconazole ziram M-257 cyproconazole guazatin M-258 cyproconazole thiophanate- methyl M-259 cyproconazole chlorothalonil M-260 cyproconazole metrafenone M-261 epoxiconazole — M-262 epoxiconazole fenbuconazole M-263 epoxiconazole fluquinconazole M-264 epoxiconazole flutriafol M-265 epoxiconazole ipconazole M-266 epoxiconazole metconazole M-267 epoxiconazole propiconazole M-268 epoxiconazole prothioconazole M-269 epoxiconazole tebuconazole M-270 epoxiconazole triadimenol M-271 epoxiconazole triticonazole M-272 epoxiconazole imazalil M-273 epoxiconazole prochloraz M-274 epoxiconazole carbendazim M-275 epoxiconazole thiabendazole M-276 epoxiconazole ethaboxam M-277 epoxiconazole hymexazole M-278 epoxiconazole pyrimethanil M-279 epoxiconazole fludioxonil M-280 epoxiconazole aldimorph M-281 epoxiconazole dodemorph M-282 epoxiconazole fenpropimorph M-283 epoxiconazole iprodione M-284 epoxiconazole captan M-285 epoxiconazole fenoxanil M-286 epoxiconazole probenazol M-287 epoxiconazole mancozeb M-288 epoxiconazole metiram M-289 epoxiconazole thiram M-290 epoxiconazole ziram M-291 epoxiconazole guazatin M-292 epoxiconazole thiophanate- methyl M-293 epoxiconazole chlorothalonil M-294 epoxiconazole metrafenone M-295 fenbuconazole — M-296 fenbuconazole fluquinconazole M-297 fenbuconazole flutriafol M-298 fenbuconazole ipconazole M-299 fenbuconazole metconazole M-300 fenbuconazole propiconazole M-301 fenbuconazole prothioconazole M-302 fenbuconazole tebuconazole M-303 fenbuconazole triadimenol M-304 fenbuconazole triticonazole M-305 fenbuconazole imazalil M-306 fenbuconazole prochloraz M-307 fenbuconazole carbendazim M-308 fenbuconazole thiabendazole M-309 fenbuconazole ethaboxam M-310 fenbuconazole hymexazole M-311 fenbuconazole pyrimethanil M-312 fenbuconazole fludioxonil M-313 fenbuconazole aldimorph M-314 fenbuconazole dodemorph M-315 fenbuconazole fenpropimorph M-316 fenbuconazole iprodione M-317 fenbuconazole captan M-318 fenbuconazole fenoxanil M-319 fenbuconazole probenazol M-320 fenbuconazole mancozeb M-321 fenbuconazole metiram M-322 fenbuconazole thiram M-323 fenbuconazole ziram M-324 fenbuconazole guazatin M-325 fenbuconazole thiophanate- methyl M-326 fenbuconazole chlorothalonil M-327 fenbuconazole metrafenone M-328 fluquinconazole — M-329 fluquinconazole flutriafol M-330 fluquinconazole ipconazole M-331 fluquinconazole metconazole M-332 fluquinconazole propiconazole M-333 fluquinconazole prothioconazole M-334 fluquinconazole tebuconazole M-335 fluquinconazole triadimenol M-336 fluquinconazole triticonazole M-337 fluquinconazole imazalil M-338 fluquinconazole prochloraz M-339 fluquinconazole carbendazim M-340 fluquinconazole thiabendazole M-341 fluquinconazole ethaboxam M-342 fluquinconazole hymexazole M-343 fluquinconazole pyrimethanil M-344 fluquinconazole fludioxonil M-345 fluquinconazole aldimorph M-346 fluquinconazole dodemorph M-347 fluquinconazole fenpropimorph M-348 fluquinconazole iprodione M-349 fluquinconazole captan M-350 fluquinconazole fenoxanil M-351 fluquinconazole probenazol M-352 fluquinconazole mancozeb M-353 fluquinconazole metiram M-354 fluquinconazole thiram M-355 fluquinconazole ziram M-356 fluquinconazole guazatin M-357 fluquinconazole thiophanate- methyl M-358 fluquinconazole chlorothalonil M-359 fluquinconazole metrafenone M-360 flutriafol — M-361 flutriafol ipconazole M-362 flutriafol metconazole M-363 flutriafol propiconazole M-364 flutriafol prothioconazole M-365 flutriafol tebuconazole M-366 flutriafol triadimenol M-367 flutriafol triticonazole M-368 flutriafol imazalil M-369 flutriafol prochloraz M-370 flutriafol carbendazim M-371 flutriafol thiabendazole M-372 flutriafol ethaboxam M-373 flutriafol hymexazole M-374 flutriafol pyrimethanil M-375 flutriafol fludioxonil M-376 flutriafol aldimorph M-377 flutriafol dodemorph M-378 flutriafol fenpropimorph M-379 flutriafol iprodione M-380 flutriafol captan M-381 flutriafol fenoxanil M-382 flutriafol probenazol M-383 flutriafol mancozeb M-384 flutriafol metiram M-385 flutriafol thiram M-386 flutriafol ziram M-387 flutriafol guazatin M-388 flutriafol thiophanate- methyl M-389 flutriafol chlorothalonil M-390 flutriafol metrafenone M-391 ipconazole — M-392 ipconazole metconazole M-393 ipconazole propiconazole M-394 ipconazole prothioconazole M-395 ipconazole tebuconazole M-396 ipconazole triadimenol M-397 ipconazole triticonazole M-398 ipconazole imazalil M-399 ipconazole prochloraz M-400 ipconazole carbendazim M-401 ipconazole thiabendazole M-402 ipconazole ethaboxam M-403 ipconazole hymexazole M-404 ipconazole pyrimethanil M-405 ipconazole fludioxonil M-406 ipconazole aldimorph M-407 ipconazole dodemorph M-408 ipconazole fenpropimorph M-409 ipconazole iprodione M-410 ipconazole captan M-411 ipconazole fenoxanil M-412 ipconazole probenazol M-413 ipconazole mancozeb M-414 ipconazole metiram M-415 ipconazole thiram M-416 ipconazole ziram M-417 ipconazole guazatin M-418 ipconazole thiophanate- methyl M-419 ipconazole chlorothalonil M-420 ipconazole metrafenone M-421 metconazole — M-422 metconazole propiconazole M-423 metconazole prothioconazole M-424 metconazole tebuconazole M-425 metconazole triadimenol M-426 metconazole triticonazole M-427 metconazole imazalil M-428 metconazole prochloraz M-429 metconazole carbendazim M-430 metconazole thiabendazole M-431 metconazole ethaboxam M-432 metconazole hymexazole M-433 metconazole pyrimethanil M-434 metconazole fludioxonil M-435 metconazole aldimorph M-436 metconazole dodemorph M-437 metconazole fenpropimorph M-438 metconazole iprodione M-439 metconazole captan M-440 metconazole fenoxanil M-441 metconazole probenazol M-442 metconazole mancozeb M-443 metconazole metiram M-444 metconazole thiram M-445 metconazole ziram M-446 metconazole guazatin M-447 metconazole thiophanate- methyl M-448 metconazole chlorothalonil M-449 metconazole metrafenone M-450 propiconazole — M-451 propiconazole prothioconazole M-452 propiconazole tebuconazole M-453 propiconazole triadimenol M-454 propiconazole triticonazole M-455 propiconazole imazalil M-456 propiconazole prochloraz M-457 propiconazole carbendazim M-458 propiconazole thiabendazole M-459 propiconazole ethaboxam M-460 propiconazole hymexazole M-461 propiconazole pyrimethanil M-462 propiconazole fludioxonil M-463 propiconazole aldimorph M-464 propiconazole dodemorph M-465 propiconazole fenpropimorph M-466 propiconazole iprodione M-467 propiconazole captan M-468 propiconazole fenoxanil M-469 propiconazole probenazol M-470 propiconazole mancozeb M-471 propiconazole metiram M-472 propiconazole thiram M-473 propiconazole ziram M-474 propiconazole guazatin M-475 propiconazole thiophanate- methyl M-476 propiconazole chlorothalonil M-477 propiconazole metrafenone M-478 prothioconazole — M-479 prothioconazole tebuconazole M-480 prothioconazole triadimenol M-481 prothioconazole triticonazole M-482 prothioconazole imazalil M-483 prothioconazole prochloraz M-484 prothioconazole carbendazim M-485 prothioconazole thiabendazole M-486 prothioconazole ethaboxam M-487 prothioconazole hymexazole M-488 prothioconazole pyrimethanil M-489 prothioconazole fludioxonil M-490 prothioconazole aldimorph M-491 prothioconazole dodemorph M-492 prothioconazole fenpropimorph M-493 prothioconazole iprodione M-494 prothioconazole captan M-495 prothioconazole fenoxanil M-496 prothioconazole probenazol M-497 prothioconazole mancozeb M-498 prothioconazole metiram M-499 prothioconazole thiram M-500 prothioconazole ziram M-501 prothioconazole guazatin M-502 prothioconazole thiophanate- methyl M-503 prothioconazole chlorothalonil M-504 prothioconazole metrafenone M-505 tebuconazole — M-506 tebuconazole triadimenol M-507 tebuconazole triticonazole M-508 tebuconazole imazalil M-509 tebuconazole prochloraz M-510 tebuconazole carbendazim M-511 tebuconazole thiabendazole M-512 tebuconazole ethaboxam M-513 tebuconazole hymexazole M-514 tebuconazole pyrimethanil M-515 tebuconazole fludioxonil M-516 tebuconazole aldimorph M-517 tebuconazole dodemorph M-518 tebuconazole fenpropimorph M-519 tebuconazole iprodione M-520 tebuconazole captan M-521 tebuconazole fenoxanil M-522 tebuconazole probenazol M-523 tebuconazole mancozeb M-524 tebuconazole metiram M-525 tebuconazole thiram M-526 tebuconazole ziram M-527 tebuconazole guazatin M-528 tebuconazole thiophanate- methyl M-529 tebuconazole chlorothalonil M-530 tebuconazole metrafenone M-531 triadimenol — M-532 triadimenol triticonazole M-533 triadimenol imazalil M-534 triadimenol prochloraz M-535 triadimenol carbendazim M-536 triadimenol thiabendazole M-537 triadimenol ethaboxam M-538 triadimenol hymexazole M-539 triadimenol pyrimethanil M-540 triadimenol fludioxonil M-541 triadimenol aldimorph M-542 triadimenol dodemorph M-543 triadimenol fenpropimorph M-544 triadimenol iprodione M-545 triadimenol captan M-546 triadimenol fenoxanil M-547 triadimenol probenazol M-548 triadimenol mancozeb M-549 triadimenol metiram M-550 triadimenol thiram M-551 triadimenol ziram M-552 triadimenol guazatin M-553 triadimenol thiophanate- methyl M-554 triadimenol chlorothalonil M-555 triadimenol metrafenone M-556 triticonazole — M-557 triticonazole imazalil M-558 triticonazole prochloraz M-559 triticonazole carbendazim M-560 triticonazole thiabendazole M-561 triticonazole ethaboxam M-562 triticonazole hymexazole M-563 triticonazole pyrimethanil M-564 triticonazole fludioxonil M-565 triticonazole aldimorph M-566 triticonazole dodemorph M-567 triticonazole fenpropimorph M-568 triticonazole iprodione M-569 triticonazole captan M-570 triticonazole fenoxanil M-571 triticonazole probenazol M-572 triticonazole mancozeb M-573 triticonazole metiram M-574 triticonazole thiram M-575 triticonazole ziram M-576 triticonazole guazatin M-577 triticonazole thiophanate- methyl M-578 triticonazole chlorothalonil M-579 triticonazole metrafenone M-580 imazalil — M-581 imazalil prochloraz M-582 imazalil carbendazim M-583 imazalil thiabendazole M-584 imazalil ethaboxam M-585 imazalil hymexazole M-586 imazalil pyrimethanil M-587 imazalil fludioxonil M-588 imazalil aldimorph M-589 imazalil dodemorph M-590 imazalil fenpropimorph M-591 imazalil iprodione M-592 imazalil captan M-593 imazalil fenoxanil M-594 imazalil probenazol M-595 imazalil mancozeb M-596 imazalil metiram M-597 imazalil thiram M-598 imazalil ziram M-599 imazalil guazatin M-600 imazalil thiophanate- methyl M-601 imazalil chlorothalonil M-602 imazalil metrafenone M-603 prochloraz — M-604 prochloraz carbendazim M-605 prochloraz thiabendazole M-606 prochloraz ethaboxam M-607 prochloraz hymexazole M-608 prochloraz pyrimethanil M-609 prochloraz fludioxonil M-610 prochloraz aldimorph M-611 prochloraz dodemorph M-612 prochloraz fenpropimorph M-613 prochloraz iprodione M-614 prochloraz captan M-615 prochloraz fenoxanil M-616 prochloraz probenazol M-617 prochloraz mancozeb M-618 prochloraz metiram M-619 prochloraz thiram M-620 prochloraz ziram M-621 prochloraz guazatin M-622 prochloraz thiophanate- methyl M-623 prochloraz chlorothalonil M-624 prochloraz metrafenone M-625 carbendazim — M-626 carbendazim thiabendazole M-627 carbendazim ethaboxam M-628 carbendazim hymexazole M-629 carbendazim pyrimethanil M-630 carbendazim fludioxonil M-631 carbendazim aldimorph M-632 carbendazim dodemorph M-633 carbendazim fenpropimorph M-634 carbendazim iprodione M-635 carbendazim captan M-636 carbendazim fenoxanil M-637 carbendazim probenazol M-638 carbendazim mancozeb M-639 carbendazim metiram M-640 carbendazim thiram M-641 carbendazim ziram M-642 carbendazim guazatin M-643 carbendazim thiophanate- methyl M-644 carbendazim chlorothalonil M-645 carbendazim metrafenone M-646 thiabendazole — M-647 thiabendazole ethaboxam M-648 thiabendazole hymexazole M-649 thiabendazole pyrimethanil M-650 thiabendazole fludioxonil M-651 thiabendazole aldimorph M-652 thiabendazole dodemorph M-653 thiabendazole fenpropimorph M-654 thiabendazole iprodione M-655 thiabendazole captan M-656 thiabendazole fenoxanil M-657 thiabendazole probenazol M-658 thiabendazole mancozeb M-659 thiabendazole metiram M-660 thiabendazole thiram M-661 thiabendazole ziram M-662 thiabendazole guazatin M-663 thiabendazole thiophanate- methyl M-664 thiabendazole chlorothalonil M-665 thiabendazole metrafenone M-666 ethaboxam — M-667 ethaboxam hymexazole M-668 ethaboxam pyrimethanil M-669 ethaboxam fludioxonil M-670 ethaboxam aldimorph M-671 ethaboxam dodemorph M-672 ethaboxam fenpropimorph M-673 ethaboxam iprodione M-674 ethaboxam captan M-675 ethaboxam fenoxanil M-676 ethaboxam probenazol M-677 ethaboxam mancozeb M-678 ethaboxam metiram M-679 ethaboxam thiram M-680 ethaboxam ziram M-681 ethaboxam guazatin M-682 ethaboxam thiophanate- methyl M-683 ethaboxam chlorothalonil M-684 ethaboxam metrafenone M-685 hymexazole — M-686 hymexazole pyrimethanil M-687 hymexazole fludioxonil M-688 hymexazole aldimorph M-689 hymexazole dodemorph M-690 hymexazole fenpropimorph M-691 hymexazole iprodione M-692 hymexazole captan M-693 hymexazole fenoxanil M-694 hymexazole probenazol M-695 hymexazole mancozeb M-696 hymexazole metiram M-697 hymexazole thiram M-698 hymexazole ziram M-699 hymexazole guazatin M-700 hymexazole thiophanate- methyl M-701 hymexazole chlorothalonil M-702 hymexazole metrafenone M-703 pyrimethanil — M-704 pyrimethanil fludioxonil M-705 pyrimethanil aldimorph M-706 pyrimethanil dodemorph M-707 pyrimethanil fenpropimorph M-708 pyrimethanil iprodione M-709 pyrimethanil captan M-710 pyrimethanil fenoxanil M-711 pyrimethanil probenazol M-712 pyrimethanil mancozeb M-713 pyrimethanil metiram M-714 pyrimethanil thiram M-715 pyrimethanil ziram M-716 pyrimethanil guazatin M-717 pyrimethanil thiophanate- methyl M-718 pyrimethanil chlorothalonil M-719 pyrimethanil metrafenone M-720 fludioxonil — M-721 fludioxonil aldimorph M-722 fludioxonil dodemorph M-723 fludioxonil fenpropimorph M-724 fludioxonil iprodione M-725 fludioxonil captan M-726 fludioxonil fenoxanil M-727 fludioxonil probenazol M-728 fludioxonil mancozeb M-729 fludioxonil metiram M-730 fludioxonil thiram M-731 fludioxonil ziram M-732 fludioxonil guazatin M-733 fludioxonil thiophanate- methyl M-734 fludioxonil chlorothalonil M-735 fludioxonil metrafenone M-736 aldimorph — M-737 aldimorph dodemorph M-738 aldimorph fenpropimorph M-739 aldimorph iprodione M-740 aldimorph captan M-741 aldimorph fenoxanil M-742 aldimorph probenazol M-743 aldimorph mancozeb M-744 aldimorph metiram M-745 aldimorph thiram M-746 aldimorph ziram M-747 aldimorph guazatin M-748 aldimorph thiophanate- methyl M-749 aldimorph chlorothalonil M-750 aldimorph metrafenone M-751 dodemorph — M-752 dodemorph fenpropimorph M-753 dodemorph iprodione M-754 dodemorph captan M-755 dodemorph fenoxanil M-756 dodemorph probenazol M-757 dodemorph mancozeb M-758 dodemorph metiram M-759 dodemorph thiram M-760 dodemorph ziram M-761 dodemorph guazatin M-762 dodemorph thiophanate- methyl M-763 dodemorph chlorothalonil M-764 dodemorph metrafenone M-765 fenpropimorph — M-766 fenpropimorph iprodione M-767 fenpropimorph captan M-768 fenpropimorph fenoxanil M-769 fenpropimorph probenazol M-770 fenpropimorph mancozeb M-771 fenpropimorph metiram M-772 fenpropimorph thiram M-773 fenpropimorph ziram M-774 fenpropimorph guazatin M-775 fenpropimorph thiophanate- methyl M-776 fenpropimorph chlorothalonil M-777 fenpropimorph metrafenone M-778 iprodione — M-779 iprodione captan M-780 iprodione fenoxanil M-781 iprodione probenazol M-782 iprodione mancozeb M-783 iprodione metiram M-784 iprodione thiram M-785 iprodione ziram M-786 iprodione guazatin M-787 iprodione thiophanate- methyl M-788 iprodione chlorothalonil M-789 iprodione metrafenone M-790 captan — M-791 captan fenoxanil M-792 captan probenazol M-793 captan mancozeb M-794 captan metiram M-795 captan thiram M-796 captan ziram M-797 captan guazatin M-798 captan thiophanate- methyl M-799 captan chlorothalonil M-800 captan metrafenone M-801 fenoxanil — M-802 fenoxanil probenazol M-803 fenoxanil mancozeb M-804 fenoxanil metiram M-805 fenoxanil thiram M-806 fenoxanil ziram M-807 fenoxanil guazatin M-808 fenoxanil thiophanate- methyl M-809 fenoxanil chlorothalonil M-810 fenoxanil metrafenone M-811 probenazol — M-812 probenazol mancozeb M-813 probenazol metiram M-814 probenazol thiram M-815 probenazol ziram M-816 probenazol guazatin M-817 probenazol thiophanate- methyl M-818 probenazol chlorothalonil M-819 probenazol metrafenone M-820 mancozeb — M-821 mancozeb metiram M-822 mancozeb thiram M-823 mancozeb ziram M-824 mancozeb guazatin M-825 mancozeb thiophanate- methyl M-826 mancozeb chlorothalonil M-827 mancozeb metrafenone M-828 metiram — M-829 metiram thiram M-830 metiram ziram M-831 metiram guazatin M-832 metiram thiophanate- methyl M-833 metiram chlorothalonil M-834 metiram metrafenone M-835 thiram — M-836 thiram ziram M-837 thiram guazatin M-838 thiram thiophanate- methyl M-839 thiram chlorothalonil M-840 thiram metrafenone M-841 ziram — M-842 ziram guazatin M-843 ziram thiophanate- methyl M-844 ziram chlorothalonil M-845 ziram metrafenone M-846 guazatin — M-847 guazatin thiophanate- methyl M-848 guazatin chlorothalonil M-849 guazatin metrafenone M-850 thiophanate- — methyl M-851 thiophanate- chlorothalonil methyl M-852 thiophanate- metrafenone methyl M-853 chlorothalonil — M-854 chlorothalonil metrafenone M-855 metrafenone —

The crystalline modification II and the one or more compound(s) of groups A.1-A.15 are usually applied in a weight ratio of from 500:1 to 1:100, preferably from 20:1 to 1:50, in particular from 5:1 to 1:20.

The afore-mentioned applies also to the ratios of combinations of modification II with fungicidal compounds IIA. Compounds IIB are usually combined with modification II in ratios from 100:1 to 1:100.

Depending on the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 750 g/ha.

The crystalline modification II, the mixtures and the compositions according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the crystalline modification II, the mixtures or the compositions according to the invention.

“Locus” means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.

In general, “pesticidally effective amount” means the amount of the crystalline modification II, the mixtures and the compositions according to the invention needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures/compositions used in the invention. A pesticidally effective amount of the mixtures/compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

The crystalline modification II, the mixtures and the compositions according to the invention can also be employed for protecting plants from attack or infestation by insects, acarids or nematodes comprising contacting a plant, or soil or water in which the plant is growing.

In the context of the present invention, the term plant refers to an entire plant, a part of the plant or the propagation material of the plant, that is, the seed or the seedling.

Plants which can be treated with the crystalline modification II, the mixtures and the compositions according to the invention include all genetically modified plants or transgenic plants, e.g. crops which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods, or plants which have modified characteristics in comparison with existing plants, which can be generated for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures.

Some of the inventive mixtures and compositions have systemic action and can therefore be used for the protection of the plant shoot against foliar pests as well as for the treatment of the seed and roots against soil pests. The term seed treatment comprises all suitable seed treatment techniques known in the art, such as, but not limited to, seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting.

The present invention also comprises seeds coated with or containing the crystalline modification II or the mixtures or the compositions according to the invention.

The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.

Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize/sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the crystalline modification II, the mixtures and the compositions according to the invention may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides or nematicides owing to breeding, mutation and/or genetic engineering methods.

For example, the crystalline modification II, the mixtures and the compositions according to the invention can be employed in transgenic crops which are resistant to herbicides from the group consisting of the sulfonylureas (EP-A-0257993, U.S. Pat. No. 5,013,659), imidazolinones (see for example U.S. Pat. No. 6,222,100, WO0182685, WO0026390, WO9741218, WO9802526, WO9802527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073), glufosinate-type (see for example EP-A-0242236, EP-A-242246) or glyphosate-type (see for example WO 92/00377) or in plants resistant towards herbicides selected from the group of cyclohexadienone/aryloxyphenoxypropionic acid herbicides (U.S. Pat. Nos. 5,162,602, 5,290,696, 5,498,544, 5,428,001, 6,069,298, 6,268,550, 6,146,867, 6,222,099, 6,414,222) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259).

Furthermore, the crystalline modification II, the mixtures and the compositions according to the invention can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated, for example by traditional breeding methods and/or the generation of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).

The seed treatment application of the crystalline modification II, the mixtures and the compositions according to the invention is carried out by spraying or dusting the seeds before sowing of the plants and before emergence of the plants.

In the treatment of seeds the corresponding formulations are applied by treating the seeds with an effective amount of the crystalline modification II, the mixtures or the compositions according to the invention. Herein, the application rates of the crystalline modification II are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 2.5 kg per 100 kg of seed. For specific crops such as lettuce and onions the rates can be higher.

The mixtures and the compositions according to the invention are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into water, on floor, wall, or by perimeter spray application and bait.

According to another preferred embodiment of the invention, for use against non-crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the mixtures and the compositions according to the invention are prepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the mixtures/compositions is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitoes, crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding stimulants or para and/or sex pheromones readily known in the art.

Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with the inventive mixtures and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a composition including the inventive mixtures, optionally a repellent and at least one binder.

The crystalline modification II, the mixtures and the compositions according to the invention can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).

In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m² treated material, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.

For use in bait compositions, the typical content of active ingredient(s) is from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound. The composition used may also comprise other additives such as a solvent of the active material, a flavoring agent, a preserving agent, a dye or a bitter agent. Its attractiveness may also be enhanced by a special color, shape or texture.

For use in spray compositions, the content of the active ingredient(s) is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the active ingredient(s) may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

It was also an object of the present invention to provide mixtures suitable for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests. Problems that may be encountered with pest control on or in animals and/or humans are similar to those described at the outset, namely the need for reduced dosage rates, and/or enhanced spectrum of activity and/or combination of knock-down activity with prolonged control and/or resistance management.

This invention also provides a method for treating, controlling, preventing and protecting warm-blooded animals, including humans, and fish against infestation and infection by pests of the orders Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera, which comprises orally, topically or parenterally administering or applying to said animals a pesticidally effective amount of the crystalline modification II, the mixtures and the compositions according to the invention.

The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting a warm-blooded animal or a fish against infestation or infection by pests of the Siphonaptera, Hymenoptera, Hemiptera, Orthoptera, Acarina, Phthiraptera, and Diptera orders which comprises a pesticidally effective amount of the crystalline modification II, the mixtures and the compositions according to the invention.

The above method is particularly useful for controlling and preventing infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, goats, dogs and cats as well as humans.

Infestations in warm-blooded animals and fish including, but not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas may be controlled, prevented or eliminated by the crystalline modification II, the mixtures and the compositions according to the invention.

For oral administration to warm-blooded animals, the crystalline modification II, the mixtures and the compositions according to the invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the crystalline modification II, the mixtures and the compositions according to the invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the crystalline modification II, the mixtures and the compositions according to the invention.

Alternatively, the crystalline modification II, the mixtures and the compositions according to the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The crystalline modification II, the mixtures and the compositions according to the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the crystalline modification II, the mixtures and the compositions according to the invention may be formulated into an implant for subcutaneous administration. In addition, the crystalline modification II, the mixtures and the compositions according to the invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the crystalline modification II, the mixtures and the compositions according to the invention.

The crystalline modification II, the mixtures and the compositions according to the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, spot-on and pour-on formulations. For topical application, dips and sprays usually contain 0.5 ppm to 5000 ppm and preferably 1 ppm to 3000 ppm of the crystalline modification II. In addition, the crystalline modification II may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.

The figure and examples below serve to illustrate the invention and are not to be understood as limiting it.

FIG. 1: X-ray powder diffractogram of modification II

FIG. 2: Differential scanning calorimetry thermogram of modification II

FIG. 3: Thermogravimetric analysis of modification II

FIG. 4: X-ray powder diffractograms of mixtures of modifications I and V

PREPARATION EXAMPLES Example 1 Characterization of a Solid Form of Fipronil as Starting Material

All preparation procedures below were conducted with two samples of solid fipronil as starting materials which were obtained according to procedures as described in WO 2001/30760, with final crystallization of the product from a solvent mixture of MCB/ethanole (% by weight of ethanol at crystallization start: 13%) at temperatures of 70° C. to 35° C. This solid form in X-ray powder diffractogram studies proved to be crystalline fipronil of a mixture of several crystalline modifications. This mixture has been characterized to consist of crystalline modification I and crystalline modification V, as for the first time identified and described in a co-pending patent application. A least squares refinement with the Topas program with simulated X-ray powder diffractogram patterns from single crystal data of form I and form V shows that in these two example samples, the percentage of form I varies from 30% to 70%. X-ray powder diffractograms of the two samples are shown in FIG. 4.

Irrespective of the sample of solid fipronil used as starting material, the crystallization examples given below yielded in modification II.

Example 2 Preparation of Modification II by Crystallization from THF

1.0 g of crystalline fipronil having a chemical purity of about 96% by weight was dissolved in 25 ml of THF at 45 to 50° C.[_(B7)] in a round bottomed flask. The solution was kept at this temperature while the solvent was slowly evaporated with a gentle flow of inert N₂ gas. The solvent was left to evaporate for about 15 hours, after which the obtained crystalline material was filtered from some residual solvent on a paper filter. The material obtained has the X-ray powder diffractogram shown in FIG. 1 with the reflexes listed in Table 2 below.

Example 3 Preparation of Modification II by Crystallization from 1,2-Dichloroethane (DCE)

1.0 g of crystalline fipronil having a chemical purity of about 96% by weight was dissolved in 25 ml of DCE at 45° C. to 50° C. in a round bottomed flask. Then the heating was switched off and the oil bath was left to cool to 20° C. to 25° C. The solvent was left to evaporate for about 15 hours. The material obtained has the X-ray powder diffractogram shown in FIG. 1 with the reflexes listed in Table 2 below.

Example 4 Preparation of Modification II by Crystallization from Acetonitrile

2.0 g of crystalline fipronil having a chemical purity of about 96% by weight was dissolved in 4 ml of acetonitrile at 75° C. to 80° C. in a 10 ml test tube to give a clear solution. The solution was cooled down to 5° C. in approximately 8 h and left at 5° C. over night. The supernatant was removed by using a pipet. The solid was dried on a filter paper for a few hours and then analyzed to give within a 0.3° 2θ error marginal the X-ray powder diffractogram shown in FIG. 1.

Example 5 Preparation of Modification II by Crystallization from Toluene

0.7 g of fipronil having chemical purity of >98% by weight was suspended in 10 ml of toluene in a 30 ml glass reactor. Stirring was applied and the suspension was heated up to 110° C. where the solid was completely dissolved. The solution was then cooled down to 25° C. with a cooling rate of −1 K/min. The crystallization was observed to begin at 86° C. The solid product was filtrated and dried on filtration paper over night and then analyzed to give within a 0.3° 2θ error marginal the X-ray powder diffractogram shown in FIG. 1. The content of fipronil in this experiment was 8.2 w-%.

Example 6 Preparation of Modification II by Crystallization from Monochlorobenzene (MCB)

0.60 g of fipronil having chemical purity of >98% by weight was suspended in 15 ml of MCB. Stirring was applied and the suspension was heated up to 137° C. where the solid was completely dissolved. The solution was then cooled down to 25° C. with a cooling rate of −1 K/min. The crystallization was observed to begin at 76° C. The solid product was filtrated and dried on filtration paper over night and then analyzed to give within a 0.3° 2θ error marginal the X-ray powder diffractogram shown in FIG. 1.

Example 7 Preparation of Modification II by Crystallization from Mesitylene

2 g of fipronil having chemical purity of ˜96% by weight was dissolved at 15 ml of mesitylene. The solution was cooled down within 5 hours to 20-25° C. and left to stand over night. The crystallized solid was filtered and dried in a vacuum oven (at 10 mbar) for ˜1.5 h at 40° C. The sample was analyzed to give within a 0.3° 2θ error marginal the X-ray powder diffractogram shown in FIG. 1[_(B8)].

Example 8 Preparation of Modification II by Crystallization from Nitrobenzene

2 g of fipronil having chemical purity of about 96% by weight was dissolved at 5 ml of nitrobenzene. The solution was cooled down within 5 hours to 20-25° C. and left to stand over night. The crystallized solid was filtered and dried in a vacuum oven (at 10 mbar) for about 1.5 h at 40° C. The sample was analyzed to give within a 0.3° 2θ error marginal the X-ray powder diffractogram shown in FIG. 1[_(B9)].

Example 9 Preparation of Modification II by Crystallization from Ethyl Benzene

1.5 g of fipronil having chemical purity of >98% by weight was suspended in 10 ml of ethyl benzene. Stirring was applied and the suspension was heated up to 136° C. giving a clear solution. The solution was cooled down to 25° C. with a cooling rate of −1 K/min. The crystallization was detected to begin at 118° C. The solid product was filtrated and dried on filtration paper over night and then analyzed to give within a 0.3° 2θ error marginal the X-ray powder diffractogram shown in FIG. 1.

Example 10 Preparation of Modification II by Crystallization from CF₃-Benzene

1.5 g of fipronil having chemical purity of >98% by weight was suspended in 18.5 ml of CF₃-benzene. Stirring was applied and the suspension was heated up to 103° C. giving a clear solution. The solution was cooled down to 25° C. with a cooling rate of −1 K/min. The crystallization was detected to begin at 97° C. The solid product was filtrated and dried on filtration paper over night at 20-25° C. The sample was analyzed to be within 0.3° 2θ error marginal the X-ray powder diffractogram shown in FIG. 1.

TABLE 2 d-spacings and 2θ-angles of modification II d (Å) 2θ d = 13.44 ± 0.2 Å  6.6 ± 0.2° d = 7.84 ± 0.1 Å 11.3 ± 0.2° d = 5.50 ± 0.07 Å 16.1 ± 0.2° d = 5.14 ± 0.05 Å 17.2 ± 0.2° d = 4.95 ± 0.05 Å 17.9 ± 0.2° d = 3.95 ± 0.05 Å 22.4 ± 0.2° d = 3.77 ± 0.05 Å. 23.5 ± 0.2° d = 3.22 ± 0.03 Å 27.6 ± 0.2° d = 2.91 ± 0.03 Å 30.8 ± 0.2° Analysis:

The X-ray powder diffractogram displayed in FIG. 1 was recorded using a Siemens D-5000 diffractometer (manufacturer: Bruker AXS) in reflection geometry in the range from 2θ=2°-60° with increments of 0.02° using Cu-Kα radiation at 25° C. The 2θ values found were used to calculate the stated interplanar spacing d. In FIG. 1, the intensity of the peaks (y-axis: linear intensity in counts) is plotted versus the 2θ angle (x-axis in degrees 2θ).

The single crystal X-ray diffraction data was collected on a Bruker AXS CCD Detector using graphite Cu_(Kα) radiation. The structure was solved by using direct methods, refined, and expanded by using Fourier techniques with the SHELX software package (G.M. Sheldrick, SHELX-97, Universitát Góttingen, 1997). Absorption correction was performed with SADABS software.

Melting points indicated herein refer to values determined on a Mettler hot stage microscope and represent equilibrium melting points.

DSC was performed on a Mettler Toledo DSC 823 module in air atmosphere. Crystals taken from the mother liquor were blotted dry on filter paper and place in crimped but vented aluminum sample pans for the DCS experiment. The sample size in each case was 5 to 10 mg. The temperature range was typically 30° C. to 230° C. at a heating rate of 5° C./min.

TGA measurements were performed on a SEIKO Instrument in nitrogen atmosphere in platinum pans. The sample size in each case was ˜8-10 mg. The temperature range was 30° C. to 600° C. at a heating rate 10° C./min.

Investigations of the effect of the temperature of nucleation and beginning of the crystallization to the modification of the crystalline end product carried out with Polyblock by HEL Ltd. The multi reactor crystallization system allows the monitoring of the crystallization process and change in turbidity with special reflectance turbidity probes by HEL. The heating/cooling mantle and thermostat “Julabo FP 50” as well as the turbidity probes were controlled with a PC. 

1. A process for preparing crystalline modification II of fipronil which has an X-ray powder diffractogram showing, at 25° C., at least 5 of the following reflexes: (1) d=13.44±0.2 Å (2) d=7.84±0.1 Å (3) d=5.50±0.07 Å (4) d=5.14±0.05 Å (5) d=4.95±0.05 Å (6) d=3.95±0.05 Å (7) d=3.77±0.05 Å (8) d=3.22±0.03 Å (9) d=2.91±0.03 Å comprising: i) preparing a solution of a solid form of fipronil being different from the crystalline modification II in a solvent S selected from tetrahydrofuran and 1,2-dichloroethane; ii) effecting crystallization of fipronil; and iii) isolating the resulting precipitate.
 2. The process according to claim 1, wherein the solvent S is tetrahydrofuran.
 3. The process according to claim 1, wherein the solvent S is 1,2-dichloroethane.
 4. The process according to claim 1, wherein, in step ii), the crystallization of fipronil is effected by concentration of the solution obtained in step i).
 5. The process according to claim 1, wherein, in step ii), the crystallization of fipronil is effected by adding a solvent which reduces the solubility.
 6. The process according to claim 1, wherein step ii) is carried out in the presence of seed crystals of the crystalline modification.
 7. A crystalline modification II of fipronil which is prepared according to claim
 1. 8. The crystalline modification II according to claim 7, wherein said modification undergoes a phase transformation at 105° C. to 145° C. into two other crystalline modifications I and V of fipronil having melting points at 196 to 197° C. and at 202 to 203° C., respectively.
 9. The crystalline modification II of claim 7 having a fipronil content of at least 98% by weight.
 10. A solid fipronil comprising the crystalline modification II of claim 7 and a form of fipronil being different from crystalline modification II.
 11. The solid fipronil of claim 10, comprising the crystalline modification II in at least 85% by weight.
 12. A synergistic pesticidal or parasiticidal mixture comprising, as active components, the crystalline modification II as prepared according to claim 1 and one or more pesticidal or parasiticidal compounds.
 13. The pesticidal or parasiticidal mixture of claim 12, further comprising a pesticidally or parasiticidally acceptable carrier and/or an auxiliary.
 14. The mixture of claim 13 in the form of an aqueous suspension concentrate.
 15. The mixture of claim 13 in the form of water-dispersible granules.
 16. The mixture of claim 13 in the form of a water-dispersible powder.
 17. A method for controlling pests which comprises contacting the pests or their food supply, habitat, breeding grounds or their locus with a pesticidally effective amount of the crystalline modification II prepared according to claim
 1. 18. The method of claim 17, wherein the crystalline modification II is applied in an amount of from 5 g/ha to 2000 g/ha.
 19. A method for protecting a plant from infestation and attack by pests which comprises applying to the foliage or stem of said plant a pesticidally effective amount of the crystalline modification II prepared according to claim
 1. 20. The method of claim 19, wherein the crystalline modification II is applied in an amount of from 5 g/ha to 2000 g/ha.
 21. A method for the protection of seed comprising contacting the seed with the crystalline modification II prepared according to claim
 1. 22. The method as claimed in claim 21, wherein the crystalline modification II is applied in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 23. A seed comprising the crystalline modification II prepared according to claim 1 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
 24. A method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of the crystalline modification II prepared according to claim
 1. 